JPH06219914A - Controlling agent against underwater pest - Google Patents

Abstract

PURPOSE:To obtain a controlling agent against underwater pests, having low toxicity, residual properties, etc., and capable of manifesting effects thereof for a long period without adversely affecting an ecosystem or a working environment. CONSTITUTION:This controlling agent against underwater pests comprises one or two or more of phosphorus-containing compounds of formula I [R1 is arylalkyl; R2 is alkyl or halogenated alkyl or aryl which may be mono- or disubstituted with the alkyl; (m) is 1-3; (p) is 1 or 2; (n) is 0-2; (1) is 0 or 1, with the proviso that (m+n) is 3], e.g. compounds of formulas II and III as an active ingredient. The controlling agent is usually prepared as a coating composition or an antifouling solution, etc., for fishing nets, etc., for use. In the process, the compound of formula I is used in an amount within the range of preferably 0.5-90wt.%, especially preferably 5-80wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an underwater pest control agent for the purpose of preventing damages caused by the attachment and reproduction of pests in seawater or industrial water systems, and more specifically, ships, fishing nets, buoys, and seawater guides. The present invention provides an underwater pest control agent used for preventing adhesion of underwater pests on the surface of underwater structures such as pipes.

[0002]

BACKGROUND OF THE INVENTION Underwater structures, such as ships,
For port facilities, buoys, pipelines, bridges, offshore oilfield drilling equipment, power plant or waterway conduits, fishnets, rafts, etc., large attached flora and fauna such as barnacles, mussels, sea bream and diatoms and microbes such as bacteria. Organisms attach to the structure and cause damage such as corrosion of structures, increase in seawater frictional resistance of ships, massive death of seafood due to clogging of fishnets, sinking due to increased weight, and reduced work efficiency. In addition, in industrial water systems such as cooling water that uses natural water such as river water and lake water, and in circulating type cooling devices that use medium and tap water, bacteria, diatoms, cyanobacteria, blue-green algae, etc. abnormally propagate and water quality It causes problems such as deterioration of cooling efficiency due to deterioration and adhesion to vessel walls, blockage of water pipes, and reduction of flow rate.

In order to prevent such damage from pests in water, inorganic heavy metal compounds such as cuprous oxide, copper rhodanide and mercury oxide, or tributyltin oxide,
It has been practiced to use an antifouling agent containing an organometallic compound such as triphenyltin oxide and tributyltin (meth) acrylate polymer.

[0004]

However, these compounds which have been conventionally used are extremely toxic and require special care in handling, and also cause malformation due to accumulation in fish bodies and environmental pollution. Therefore, it has been demanded to use an antifouling agent containing neither heavy metal nor organic metal.

As antifouling agents containing neither heavy metals nor organic metals, alkylphenols (JP-A-3-12830) are used.
No. 2) or dichloro-N-phenylmaleimides (Japanese Examined Patent Publication No. 24242/1990), but these compounds are not sufficient in their effects, and in a short period of time. At present, it is not practical because the effect is lost.

[0006] Therefore, there are problems in safety and hygiene and the environment, that is, toxicity and persistence are low, which does not adversely affect the ecosystem and working environment, and which can exert its effect for a long period of time. There is a need for agents, and it is an object of the present invention to provide such pest control agents in water.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using an aquatic pest controlling agent containing a specific phosphorus-containing compound, I have found something to be achieved.

That is, the present invention provides an aquatic pesticide containing one or more compounds represented by the following general formula (I) as an active ingredient.

[0009]

[Chemical 2]

The present invention having the above-mentioned gist will be described below in more detail.

In the compound represented by the general formula (I), examples of the arylalkyl group represented by R ₁ include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, etc., and R ₂ Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, secondary octyl, tertiary octyl, nonyl. , Isononyl, tertiary nonyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triaconyl, and other straight-chain or branched alkyl groups. For example, 2-chloroethyl 1-chloro-2-propyl,
3-chloro-1-propyl, 1,3-dichloro-2-propyl, 4-chloro-1-butyl, 2,2-bis (chloromethyl) -1-propyl, 3-chloro-2,2-dimethyl- 1-propyl, 6-chloro-1-hexyl, 10
-Chloro-1-decyl, 2-bromoethyl, 1-bromo-2-propyl, 3-bromo-1-propyl, 1,3-
Dibromo-2-propyl, 2,3-dibromopropyl,
1,4-dibromo-2-butyl, 3-bromo-2-methyl-1-propyl, 3-bromo-2,2-dimethyl-1
-Propyl, 6-bromo-1-hexyl, 7-bromo-
1-heptyl, 8-bromo-1-octyl, 9-bromo-1-nonyl, 10-bromo-1-decyl, 11-bromo-1-undecyl, 12-bromo-1-dodecyl, perfluoroethyl and the like. Examples of the aryl group which may be mono- or di-substituted with the alkyl group include phenyl and naphthyl.

Some of the compounds represented by the above general formula (I) are known compounds, for example, phosphorus oxychloride,
Examples thereof include a method in which phosphorus trichloride, phosphorus pentachloride, phosphorus pentoxide, triphenyl phosphite or triphenyl phosphate and an arylalkylphenol and, if necessary, various phenols or alcohols are reacted simultaneously or sequentially.

Examples of the compound represented by the above general formula (I) used in the present invention include the following compounds.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

The present invention relates to an aquatic pest control agent containing as an active ingredient one or more compounds represented by the general formula (I), which is one of conventionally used antifouling agents or It is also possible to use it in combination with two or more kinds, and in some cases, it is possible to exert the effect for a longer period of time.

Examples of the antifouling agent which can be used in combination with the phosphorus-containing compound of the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Tetra-n-propyl thiuram disulfide, tetraisopropyl thiuram disulfide, tetra-n-butyl thiuram disulfide, tetraisoptyl thiuram disulfide, N, N'-ethylenebisthiocarbamoyl sulfide, N, N'-propylenebisthio Thiuram-based compounds such as carbamoyl sulfide and N, N'-butylenebisthiocarbamoyl sulfide; copper-based metal powders such as copper powder and copper-nickel alloy powder; cuprous oxide, cuprous thiocyanate, and basic copper carbonate. Copper compounds such as copper pyrophosphate, copper naphthenate, copper abietic acid, and copper oxyquinoline; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc ethylphenyldithiocarbamate,
Zinc ethylenebisdithiocarbamate, zinc propylenebisdithiocarbamate, zinc bis (dimethyldithiocarbamoyl) zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, etc. Dithiocarbamate compound; 2
-(4-thiazolyl) benzimidazole, methyl-1
-(Ω-cyanopentylcarbamoyl) -2-benzimidazole, 2-mercaptobenzimidazole zinc,
Benzimidazole compounds such as 2-thiocyanomethylthiobenzimidazole; 2-mercaptobenzothiazole, 2- (thiocyanomethylthio) benzothiazol
2, 2- (thiocyanomethylsulfonyl) benzothiazole, 2-thiocyanoethylthio-4-chlorobenzothiazole, 2-thiocyanopropylthio-5,7-dichlorobenzothiazole, 2-thio Cyanomethylthio-
Benzothiazole compounds such as 4,5,6,7-tetrachlorobenzothiazole; Nitrile compounds such as tetrachloroisophthalonitrile and 5-chloro-2,4-difluoro-6-methoxyisophthalonitrile 4,5
-Dichloro-2-n-octyl-4-isothiazoline-
3-one, 2-n-octyl-4-isothiazoline-3
-One, isothiazoline compounds such as 1,2-benzisothiazolin-3-one; 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolanyl-2-methyl-1-1 ( H) -1,2,4-triazole, 4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1- (4-trifluoromethyl-2)
-Chlorophenyl) -1-penten-2-ol and other triazole compounds; 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,3,6-trichloro-4-propylsulfonylpyridine, 2,6-
Pyridine compounds such as dichloro-3,5-dicyano-4-phenylpyridine; 2,4-dichloro-6- (α-chloroanilino) -s-triazine, 2-chloro-4-methylamino-6-isopropylamino-s -Triazine, 2-chloro-4,6-bis (ethylamino) -s-
Triazine, 2-chloro-4,6-bis (isopropylamino) -s-triazine, 2-methylthio-4,6-
Bis (ethylamino) -s-triazine, 2-methylthio-4-ethylamino-6-isopropylamino-s-
Triazine, 2-methylthio-4-t-butylamino-
Triazine-based compounds such as 6-cyclopropylamino-s-triazine; 3- (3,4-dichlorophenyl)-
1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea, 1- (α, α ′
-Dimethylbenzyl) -3-methyl-3-phenylurea, 1- (2-methylcyclophenyl) -3-phenylurea and other urea compounds; 2-amino-3-chloro-
Quinone compounds such as 1,4-naphthoquinone and 2,3-dicyano-1,4-dithiaanthraquinone; N-trichloromethylthiotetrahydrophthalimide, N-1,
1,2,2-tetrachloroethylthiootetrahydrophthalimide, N-trichloromethylthiophthalimide,
N-fluorodichloromethylthiophthalimide, N, N
-Dimethyl-N'-phenyl-N '-(fluorodichloromethylthio) sulfurylamide, trichloromethylthiomethanesulfone-p-chloroanilide, N- (1,
1,2,2-Tetrachloro-2-fluoroethylthio) methanesulfonanilide, N-fluorodichloromethylthio-N-3-chlorophenyl-N'-dimethylurea, N-fluorodichloromethylthio-N-3,4- N-haloalkylthio compounds such as dichlorophenyl-N'-methylurea and N-fluorodichloromethylthio-N-trissulfonyl-N-methylamine; N- (2-
Chlorophenyl) maleimide, N- (4-fluorophenyl) maleimide, N- (3,5-dichlorophenyl)
Maleimide compounds such as maleimide, N- (2,4,6-trichlorophenyl) maleimide, N-4-tolylmaleimide, N-2,4-xylylmaleimide; 3,5-
Dimethyl-tetrahydro-1,3,5,2 (H) -thiadiazin-2-one, 3,3'-ethylenebis (tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazin-2-one , 3,5-dimethyl-2-thiotetrahydro-1,3,5-thiadiazine, 3,5-dibenzyltetrahydro-1,3,5-thiadiazine-2-thione, and other thiadiazine-based compounds; methyl thiocyanide,
Chloromethyl thiocyanate, ethyl thiocyanate, methylenebisthiocyanate, chloromethylenebisthiocyanate, ethylenebisthiocyanate, chloroethylenebisthiocyanate, isobornylthiocyanate-
, Methyl isothiocyanate, allyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate and the like; caprylphenol
Phenol, nonylphenol, cumylphenol, and other phenolic compounds; tris (octylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono-dimixed nonylphenyl) Alkylphenyl phosphite compounds such as phosphite; tris (octylphenyl)
Examples thereof include alkylphenyl phosphate compounds such as phosphate, tris (nonylphenyl) phosphate, tris (dinonylphenyl) phosphate, and tris (mono-dimixed nonylphenyl) phosphate.

The aquatic pest control agent of the present invention is usually prepared and used as a coating composition or an antifouling agent liquid for fishnets and the like. In this case, the amount of the halogen-containing phosphate compound is preferably 0.5 to 90% by weight, more preferably 5 to 80%, and is appropriately selected in consideration of the purpose of use, antifouling period and the like. For example, a solution of about 80% by weight can be dipped and applied in a fish net or the like, or can be blended in a paint and applied as antifouling paint to a ship or an underwater structure.

The components used for preparing the above-mentioned coating composition or antifouling agent liquid are not particularly limited, and the components conventionally used for preparing these coating materials or antifouling agent liquid may be used as they are. it can. For example, as a resin vehicle used as an organic solvent-based paint, vinyl chloride resin, chlorinated rubber resin, chlorinated polyethylene resin, chlorinated polypropylene resin, acrylic resin, styrene-butadiene resin, polyester resin, epoxy resin, polyamide resin , Petroleum-based resin, silicone resin, silicone rubber-based resin, wax, paraffin, rosin ester, rosin-based resin, etc. can be used alone or in combination, and acrylic resin is used as a resin vehicle used as an aqueous paint. Resins, epoxy emulsion resins, vinyl acetate resins and the like can be used.

Further, together with the phosphorus-containing compound of the present invention,
The plasticizer, the coloring pigment, the filler, the solvent and the like which are usually used can be contained in an arbitrary ratio.

[0029]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples.

Example 1 Chlorinated rubber having a chlorine content of 65% (CR-2 manufactured by Asahi Denka Co., Ltd.
20 parts by weight of the sample compound was added to 100 parts by weight of the 30% xylene solution of 0), sufficiently stirred, then coated on a hard vinyl chloride plate, and dried for 24 hours to obtain a test piece.

This test piece was immersed in a test raft in Yokosuka City, Kanagawa Prefecture, at a depth of 1 m in the sea, and the degree of fouling by adherent organisms was observed over time to measure the ratio of the adhered area to the painted area. The results were evaluated according to the following criteria on a four-point scale. The results are shown in Table 1. A: Adhesion was not observed at all. B: Adhesion was recognized in a portion of 50% or less. C: Adhesion was recognized in 50% or more. D: It adhered to the entire surface and the coated surface was completely covered.

[0032]

[Table 1]

Example 2 [Composition] wt% Sample compound (Table 2) 10 Acrylic resin (50% xylene solution) * 1 20 Chlorinated paraffin * 2 1 Xylene 69 * 1: NT-100 * 2 manufactured by Nitto Kasei : Asahi Denka Kogyo Adeka Sizer E-430

The above mixture was thoroughly mixed with a high speed homomixer to prepare an antifouling agent for fishnets. Using this antifouling agent for fish nets, polyethylene test net (60 knotless twisted nodes 20 cm
(30 cm) was dyed with a dyeing net and air-dried for 2 days, and then the degree of fouling by attached organisms was examined in the same manner as in Example 1. The results are shown in Table 2.

[0035]

[Table 2]

From the results of the above-mentioned respective examples, when alkylphenol is used as a pest control agent in water, the effect is lost in a short period of time, whereas when the phosphorus-containing compound of the present invention is used, It is clear that the effect is long-lasting.

Further, the phosphorus-containing compound of the present invention is considered not to have properties such as toxicity and teratogenicity that adversely affect the ecosystem, and is extremely useful as an aquatic pest control agent that does not cause environmental pollution. It is clear that there is.

[0038]

INDUSTRIAL APPLICABILITY The aquatic pest control agent of the present invention has low safety and hygiene and environmental problems, that is, low toxicity and persistence, and does not adversely affect the ecosystem and working environment. The effect can be exerted for a long period of time.

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[Procedure amendment]

[Submission date] February 9, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[0002]

Underwater structures BACKGROUND OF INVENTION Problems to be Solved], for example, ships, port facilities, buoys, pipelines, bridges, offshore oil drilling equipment, headrace tube power plants or seaside plants, for fishing nets and farming Large adherent flora and fauna such as barnacles, mussels, and sea urchins and microscopic organisms such as diatoms and bacteria adhere to rafts, causing structure corrosion, increasing seawater friction resistance of ships, and massive death of seafood due to clogging of fishnets. Damage such as sedimentation and reduced work efficiency due to increased weight will occur. In addition, in industrial water systems such as cooling water that uses natural water such as river water and lake water, and in circulating type cooling devices that use medium and tap water, bacteria, diatoms, cyanobacteria, blue-green algae, etc. abnormally propagate and water quality It causes problems such as deterioration of cooling efficiency due to deterioration and adhesion to vessel walls, blockage of water pipes, and reduction of flow rate.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

However, these conventionally used compounds are extremely toxic, and not only require special handling, but also cause malformation due to accumulation in fish bodies and environmental pollution. It has been desired to use an antifouling agent containing no organic metal.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

[0006] Therefore, the object of the present invention is to prevent health and hygiene and environmental problems, that is, toxicity and persistence are low, which does not adversely affect the ecosystem and working environment, and the effect is long-term. An object is to provide an aquatic pest control agent that can exert its effect.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, the above object was achieved by using an aquatic pest control agent containing a specific phosphorus-containing compound. I was found to be done.

Claims (1)

[Claims] 1. An aquatic pest control agent containing, as an active ingredient, one or more compounds represented by the following general formula (I):